CN1599771A - Pre-expanded beads of flame-retardant polyolefin resin and molded object thereof by in-mold foaming - Google Patents

Pre-expanded beads of flame-retardant polyolefin resin and molded object thereof by in-mold foaming Download PDF

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CN1599771A
CN1599771A CNA028241800A CN02824180A CN1599771A CN 1599771 A CN1599771 A CN 1599771A CN A028241800 A CNA028241800 A CN A028241800A CN 02824180 A CN02824180 A CN 02824180A CN 1599771 A CN1599771 A CN 1599771A
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polyolefin resin
expanded beads
retardant
flame
expanded
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CN1309768C (en
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约翰·B·斯图尔特
史蒂文·C·斯卡克
荻田哲也
山口武马
岩本友典
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Chung Yuan Chemical Industry Usa Holding Co
Kaneka Corp
Kaneka Texas Corp
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Zhong Yuan Chemical Industry Texas Co
Kanegafuchi Chemical Industry Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/16—Making expandable particles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0028—Use of organic additives containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S521/00—Synthetic resins or natural rubbers -- part of the class 520 series
    • Y10S521/907—Nonurethane flameproofed cellular product

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Flame retardant polyolefin pre-expanded particles made of a resin composition comprising a polyolefin resin and a sterically hindered amine ether flame retardant, which can be molded with good moldability to give in-mold foamed articles which have an excellent flame resistance and do not generate harmful gas at the time of burning.

Description

Expanded molded article in flame-retardant polyolefin resin pre-expanded beads and the mould thereof
Technical field
The present invention relates to lagging material, shock-resistant packaging material, revolving container, vehicle shock absorber core, electric and electronic article component etc., particularly relate to the flame-retardant polyolefin resin pre-expanded beads that is used to make the electric and electronic article component, and with expanded molded article in this flame-retardant polyolefin resin pre-expanded beads mould that foaming obtains in mould.
Background technology
Expanded molded article in the polyacrylic mould, compare with expanded molded article in the mould of polystyrene, has the deformation-recovery rate after excellent resistance to chemical reagents, thermotolerance, shock-resistance, the compression, so, be widely used as the automobile member of vibroshock with core, side collision pad, baseboard material, shock-resistant packaging material, revolving container etc.
But, derive from the expanded molded article of polyolefins resin usually, except that having above-mentioned excellent specific property, also bring the shortcoming of easy firing and so on.Particularly, expanded molded article is compared the incendivity height with non-expanded molded article, is easy to carry out the incendiary shortcoming so have.
In recent years,, require to have flame retardant resistance or flame-out certainly property, therefore carried out extensive studies, to obtain to give the expanded molded article of the flame retardant resistance that satisfies these requirements for automobile component, material of construction and electric product parts.
As the method for giving foam (by polyolefins resin foam) flame retardant resistance with normal pressure foaming or pressure expansion manufactured, have mineral-type fire retardant, halogen fire retardant, phosphorus type flame retardant etc. mixing in resin, carry out melting mixing again under the temperature below the decomposition temperature of thermolysis type whipping agent and be molded into after the shape such as sheet, the method that the fusing point (softening temperature) that is heated to resin is above, foam more than the decomposition temperature of this whipping agent.
For example, disclose in the Te Kaiping 3-269029 communique, to contain polyolefine resin 100 weight parts, mineral-type fire retardant 30～200 weight parts such as magnesium hydroxide, the flame retardant resistance resin composition that whipping agent 0.1～15 weight part and linking agent 10 weight parts or 10 weight parts are following, after the following premolding of the decomposition temperature of whipping agent, be heated to more than the fusing point (softening temperature) of resin, pressurize more than the decomposition temperature of whipping agent, expansion ratio reaches 1.1～25 times of ground and foams, produce thus and have high fire resistance, also have excellent flexibility simultaneously, thermotolerance, mechanical characteristics, thermal insulation, the fire-retardant foaming body of electrical specification etc.
In addition, disclose in the Te Kaiping 5-331310 communique, to contain the foaminess polyolefine resin composition that polyolefine resin 100 weight parts, thermolysis type whipping agent 1～40 weight part, ammonium polyphosphate 5～50 weight parts and Zinic stearas 0.5～5 weight part constitute, after with electron beam crosslinking, carry out foamable, produce the fire-retardant foaming body that toxic gas and problem such as painted do not take place.
In addition, disclose in the Te Kaiping 7-238178 communique, will be with polyolefine resin 100 weight parts, polysiloxane compound 5～200 weight parts, whipping agent (thermal degradation type whipping agent, liquefied gas build whipping agent etc.) flame-retardant polyolefin resin foaming composition as main component, after with electron beam crosslinking, carry out foamable, produce physical strength height, outward appearance excellent flame-retardant performance foam.
Te Kaiping 3-269029 communique, Te Kaiping 5-331310 communique, in the Te Kaiping 7-238178 communique, for being provided, the polyolefin resin fire-retardant foaming body uses non-halogen fire retardant, but these foaies be by add depress or normal pressure under the hot briquetting goods, make the decomposition-type foaming agent decomposition or make the volatilization of volatile-type whipping agent, thereby make moulded products foaming and make, so, disclosed method in these documents, be difficult to by pre-expanded beads is filled in the mould, and with steam heating with carry out fusion bonding and obtain in the method for foam in the mould.That is, adopt these methods, fusion bonding between the pre-expanded beads that is difficult to reach good and good appearance.In addition and since polyolefine carry out crosslinked, so these methods are being disadvantageous aspect cost and the recycle.
It is known that the additive that cooperates in the resin exerts an influence to the bubble structure of the pre-expanded beads that obtains.When non-halogen fire retardant is coupled in the pre-expanded beads, forms in conjunction with bubble and trickle bubble and degradation problem under the formability of pre-expanded beads may take place.
On the other hand, as the method for expanded molded article flame retardant resistance in the mould of giving pre-expanded beads and the pre-expanded beads moulding being obtained, known have a following method.
For example, the foam that the mutual fusion bonding of disclosed polyolefin resin expanded particle forms in the Te Kaiping 4-363341 communique, it is on the mutual fusion bonding interface of this expanded particle, has self-extinguishing (own digestibility) foam of the thermally expandable graphite powder that works as fire retardant of 8～20 weight % of foam weight.In the method, must be in advance with the thermally expandable graphite powder attached on the pre-expanded beads, again the thermally expandable graphite powder is placed on the operation on the expanded particle interface of fusion bonding, this is complex procedures not only, and, because the thermally expandable graphite powder is attached on the pre-expanded beads surface, the problem of generation is the fusion bonding variation between the expanded particle during moulding.
In addition, disclosed in the Te Kaiping 6-192465 communique, make the expanded polyolefin particle moistening with organic liquid, make membrane-forming agent add mixing again, and carry out expanded molded article in the mould of sintering (heating and melting bonding) with well-established law with fire retardant such as bromize aromatic compound and ANTIMONY TRIOXIDE SB 203 99.8 PCT etc.And about the ratio of fire retardant, being recited as in the amount of the mixture is that benchmark reaches 4～10 weight %, produces the moulded products that is suitable for the UL94HF-1 flame retardant resistance in embodiment.
In addition, put down in writing in the Te Kaiping 7-309969 communique, contain two (alkyl oxide) tetrabromo-bisphenol based flame retardants and (or) the flame-retardant polyolefin resin expanded particle of flame retardancy synergists such as two (alkyl oxide) tetrabromo-bisphenol s based flame retardant and weisspiessglanz, and has flame retardant resistance (self-extinguishing), the expanded particle of pellet melting cohesiveness, second time of foaming and formability when having good moulding again simultaneously.And the moulded products of making among the embodiment, the content of its fire retardant are that 1.7～5 weight %, expansion ratio are that 28～32 times, oxygen index are 27～32.
Have again, a kind of flame retardant resistance pre-expanded beads is disclosed in the Te Kaiping 10-147661 communique, it contains as the ethylenebis pentabromo-biphenyl of fire retardant or ethylenebis tetrabromo phthalimide with as the weisspiessglanz of flame retardancy synergists, and, are 1～30 weight parts with respect to the amount of the polyolefin resin fire retardant of 100 weight parts.And the moulded products that produces among the embodiment is suitable for the flame retardant resistance of UL94HF-2.
Also have, the spy opens the flame-retardant polyolefin resin expanded particle of putting down in writing in the flat 9-227711 communique, and it contains 5 valency phosphatization compounds, 1～20 weight % with brominated aromatic base bromination fatty group as fire retardant.
But, halogen fire retardants such as brominated flame retardant, the problem of the toxic gases such as halide gas that happen occasionally in burning.At present, the security of fire retardant becomes problem of greatest concern as environmental problem, and restriction uses the work of some compound that toxic gases such as two English might take place when burning to carry out.For example, " Block Le-エ Application ジ エ Le マ-Network " as the エ コ ラ ベ Le of Germany, the use of the organic halogen based flame retardant that contains chlorine or bromine as the restriction object, and, " TCO95 " as the エ コ ラ ベ Le of Sweden, be object with the plastic components that surpasses 25g that uses in the electric and electronic goods, ban use of organochlorine compounds and organic bromine compounds.
Therefore, require not use the flame-retardant system of brominated flame-retardant etc.
Open in the flat 11-315067 communique the spy and to disclose a kind of compound as organic materials effective stabilizer such as polyolefine, this compound is the compound with following general formula:
R 7NH-(CH 2) 3-NR 7-CH 2-CH 2-NR 7-(CH 2) 3-NHR 7
(in the formula, R 7Be to use following formula:
The group of expression), also be effective as the fire retardant of organic materialss such as polyolefine.But, about these compounds in preexpanded particles of polylefin resin and mould thereof the application aspect the expanded molded article then without any record.Preexpanded particles of polylefin resin is filled in the mould, with steam etc. heat, fusion bonding, foaming is desirable shape in mould thus, still, when the insufficient formability of pre-expanded beads, then industrial value will descend significantly.It is known that the additive that cooperates in the polyolefin resin influences being formed with of the shape and size of bubble, the combination of bubble etc. and bubble, and, fusion bonding obstacle of the pre-expanded beads when additive may cause foaming in the generation of decline, color spot of foaming and physical strength in the mould that company's alveolation or the miniaturization because of bubble cause and the mould etc.Relevant preexpanded particles of polylefin resin is not disclosed in the Te Kaiping 11-315067 communique fully and the discovery of the application facet in the expanded molded article in mould.
The object of the present invention is to provide expanded molded article in a kind of flame-retardant polyolefin resin die, these goods can be made with good formability, and, do not produce obnoxious flavour during burning.
Another object of the present invention is to provide a kind of and do not use the halogen fire retardant, and have good flame retardant resistance and the interior expanded molded article of the flame-retardant polyolefin resin die that is comparable to expanded molded article rerum natura in the non-fire-retardantization polyolefin resin mould.
Another purpose of the present invention is to provide a kind of flame-retardant polyolefin resin pre-expanded beads that does not use halogen flame, and it can be with good formability at in-mold molding, and gives in the mould expanded molded article with excellent flame and rerum natura.
These purposes of the present invention and other purposes will be clearer from following record.
Summary of the invention
The invention provides a kind of flame-retardant polyolefin resin pre-expanded beads, it is to be made of the polyolefin resin composition that contains polyolefin resin and sterically hindered amines ethers fire retardant.
Above-mentioned sterically hindered amines ethers fire retardant, the compound of preferably using general formula (1) to represent:
R 1NHCH 2CH 2CH 2NR 2CH 2CH 2NR 3CH 2CH 2CH 2NHR 4????????????(1)
[in the formula, R 1And R 2Be with general formula (2):
Figure A0282418000081
(R in the formula 5Be that to have carbonatoms be 1～12 alkyl, R 6Be methyl, cyclohexyl or octyl group) expression s-triazine part T, R 3And R 4In a kind of be with general formula (2) expression s-triazine part T, R 3And R 4In another kind then represent hydrogen atom].
Flame-retardant polyolefin resin pre-expanded beads when preferably measuring with differential scanning calorimeter, shows two melting peaks in the DSC curve, the melting peak heat QH at high temperature side peak is 1.5～25.0J/g.
The present invention also provides expanded molded article in the flame retardant resistance mould, and these goods carry out foaming with above-mentioned flame-retardant polyolefin resin pre-expanded beads and obtain in mould.
According to the present invention, fire retardant as polyolefin resin, owing to use the non-halogen fire retardant that is called sterically hindered amines ethers fire retardant, therefore do not produce problems such as toxic gas takes place when using the halogen fire retardant, and, degradation problem under the foaming in the mould of the pre-expanded beads that company seen, bubble alveolation and miniaturization cause when also not using the mineral-type non-halogen flame retardant.In addition, pre-expanded beads is filled in the mould, with steam heating and carry out fusion bonding, when making in the mould expanded molded article thus, can gives excellent flame-retardant performance and do not damage the fusion bonding between pre-expanded beads and the outward appearance of expanded molded article.And then, because expanded molded article is to make by foaming in the mould of pre-expanded beads, so can obtain the expanded molded article of complicated shape.
Description of drawings
Fig. 1 is in order to measure fusing point (Tm), and the particle 4.2mg of propylene-ethylene random copolymers that uses ethylene content 2.5 weight %, melting index MI=6.0g/10 minute is as polyolefin resin, the DSC curve of trying to achieve.
Fig. 2 is based on the curve of melting peak heat QH measuring method at the high temperature side peak of the DSC curve that the flame-retardant polyolefin resin pre-expanded beads that obtains among the embodiment 1 is obtained, and be used to try to achieve the straight line P of QH, be to draw wire by the DSC curve that to be 0 point from low temperature side peak and the peak-to-peak slope of curve of high temperature side finish side to the high temperature side peak to obtain.
Specific embodiments
Polyolefin resin is compared with the situation of polystyrene, and advantage is excellences such as the distortion after resistance to chemical reagents, thermotolerance, the compression is restorative, so be used as the base material of pre-expanded beads in the present invention.Used in the present invention polyolefin resin is to make olefin monomer 75～100 weight % or 80～100 weight % and have other monomers 0～25 weight % or 0～20 weight % of copolymerization to carry out homopolymer or the multipolymer that polymerization obtains with olefin monomer.The ratio of olefin monomer can produce the tendency that can not fully keep used olefinic monomer characteristic during less than 75 weight %.
Object lesson as above-mentioned olefin monomer, can enumerate, for example ethene, propylene, butene-1, iso-butylene, amylene-1,3-methyl butene-1, hexene-1,4-methylpentene-1,3, the alpha-olefin of carbonatomss 2～12 such as 4-dimethyl-butene-1, heptene-1,3-methyl-hexene-1, octene-1, decylene-1 etc.These both can be used alone also and two or more can be used in combination.
As having other monomeric object lessons of copolymerization, can enumerate, for example cyclopentenes, norbornylene, 1 with above-mentioned olefin monomer, 4,5,8-dimethylene (ジ メ ノ)-1,2,3,4,4a, 8,8a, cyclic olefins such as 6-octalin, 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 1,4-hexadiene, methyl isophthalic acid, 4-hexadiene, 7-methyl isophthalic acid, dienes such as 6-octadiene etc.These both can use individually also and two or more can be used in combination.
The object lesson of the olefine kind resin that forms as other monomers that have copolymerization by above-mentioned olefin monomer with it, can enumerate, high density polyethylene(HDPE) for example, medium-density polyethylene, new LDPE (film grade), polyvinylss such as straight chain shape new LDPE (film grade), alfon, ethylene-propylene copolymer (for example, ethylene content 1～15 weight %, propylene content 85～99 weight %) acronal such as, propene-1-butene copolymer, ethylene-propylene-butylene copolymer, ethene such as ethylene-propylene-diene copolymer and (or) propylene and other monomeric multipolymers, polybutene, polypenthylene etc.Wherein, be easy to get to calmly and have evenly and the independently viewpoint consideration of the pre-expanded beads of bubble structure, preferred new LDPE (film grade), straight chain shape new LDPE (film grade), ethylene-propylene random copolymer (ethylene content 1～15 weight %, propylene content 85～99 weight %), ethylene-propylene-butylene copolymer.
The said polyolefins resinoid is from the cost aspect, each points such as recycling aspect and technology simplification consider, and are preferred uncrosslinked.
These polyolefin resins both can use separately, also two or more can be used in combination.
The said polyolefins resinoid, MI (melting index) 0.1～50g/10 minute preferably, more preferably 0.3～40g/10 minute.The MI of polyolefin resin is during less than 0.1g/10 minute, lacks mobilely when then this is resin expanded, and foaming is difficult, and when surpassing 50g/10 minute, this resin demonstrates too high flowability on the contrary, is difficult to reach highly foaming, and after the pre-expanded beads foaming tendency that shrinks is easily arranged.
For the said polyolefins resinoid, in the scope of not damaging polyolefin resin character, can also be used in combination other thermoplastic resins that can use with the polyalkenes mixed with resin as required, for example polystyrene, iolon etc.
As the preferred example of above-mentioned sterically hindered amines ethers fire retardant, can enumerate, for example the compound of general formula (1) expression:
R 1NHCH 2CH 2CH 2NR 2CH 2CH 2NR 3CH 2CH 2CH 2NHR 4????(1)
[in the formula, R 1And R 2Be s-triazine part T with general formula (2) expression:
Figure A0282418000111
(R in the formula 5For example be methyl, ethyl, propyl group, butyl, just-amyl group, just-hexyl, just-heptyl, nonyl, decyl, undecyl, dodecyl, sec.-propyl, isobutyl-, sec-butyl, the tertiary butyl, 2-ethyl-butyl, isopentyl, 1-methyl amyl, 1,3-dimethylbutyl, 1-methyl hexyl, different heptyl, 1,1,3,3-tetramethyl-amyl group, 1-methyl undecyl, 1,1,3,3,5,5-hexamethyl hexyl etc. has the alkyl of 1～12 of carbonatoms, R 6Be methyl, cyclohexyl or octyl group), R 3And R 4In a kind of be with general formula (2) expression s-triazine part T, R 3And R 4In another kind then represent hydrogen atom].Sterically hindered amines ethers fire retardant both can use separately, also two or more can be used in combination.
As the object lesson of the s-triazine part T of above-mentioned general formula (2) expression, can enumerate for example 2,4-two [(1-methoxyl group-2,2,6,6-tetramethyl piperidine-4-yl) just-butyl amino]-s-triazine, 2, two [(the 1-cyclohexyloxies (シ Network ロ ヘ キ シ Le オ キ シ)-2,2 of 4-, 6,6-tetramethyl piperidine-4-yl) just-butyl amino]-s-triazine, 2, two [(the 1-octyloxies-2,2 of 4-, 6,6-tetramethyl piperidine-4-yl) just-butyl amino]-the s-triazine etc.
As the object lesson of the sterically hindered amines ethers fire retardant of above-mentioned general formula (1) expression, can enumerate N for example, N ', N -3 2, two [(the 1-cyclohexyloxies-2,2 of 4-, 6,6-tetramethyl piperidine-4-yl) just-butyl amino]-s-triazine-6-yl }-3,3 '-ethylene imino-propyl group amine; N, N ', N "-three { 2,4-two [(1-cyclohexyloxy-2,2,6,6-tetramethyl piperidines-4-yl) just-butyl amino]-s-triazine-6-yl }-3,3 '-ethylene imino-dipropylamine; N, N ', N -three { 2,4-two [(1-octyloxy-2,2,6,6-tetramethyl piperidines-4-yl) just-butyl amino]-s-triazine-6-yl }-3,3 '-ethylene imino-dipropylamine; N, N ', N "-three { 2,4-two [(1-octyloxy-2,2,6,6-tetramethyl piperidines-4-yl) just-butyl amino]-s-triazine-6-yl }-3,3 '-ethylene imino-propyl group amine; N, N ', N -three { 2,4-two [(1-methoxyl group-2,2,6,6-tetramethyl piperidines-4-yl) just-butyl amino]-s-triazine-6-yl }-3,3 '-ethylene imino-propyl group amine; N, N ', N "-three { 2,4-two [(1-methoxyl group-2,2,6,6-tetramethyl piperidines-4-yl) just-butyl amino]-s-triazine-6-yl }-3,3 '-ethylene imino-propyl group amine etc.These both can use separately, also two or more can be used in combination.
As the proportioning of said polyolefins resinoid and sterically hindered amines ethers fire retardant, with respect to polyolefin resin 100 weight parts, sterically hindered amines ethers fire retardant is 1～20 weight part, preferred 2～10 weight parts.The proportioning of above-mentioned fire retardant is difficult to obtain sufficient flame retardant resistance during less than 1 weight part, and when surpassing 20 weight parts, there is the miniaturization of becoming tendency in the aperture, and not only interior foaming, particularly appearance of mould has the tendency of deterioration, cost rises, and is disadvantageous economically.
In the composition that contains said polyolefins resinoid and sterically hindered amines ethers fire retardant, can also be as required, add for example flame retardancy synergists such as stablizer, lubricant, tinting material, UV light absorber, antistatic agent, weisspiessglanz etc. of filler, other additives.
By the pre-expanded beads that the polyolefin resin composition that contains sterically hindered amines ethers fire retardant of the present invention constitutes, can adopt known method manufacturing.For example, by with polyolefin resin with fire retardant and the additive that adds as required carry out melting mixing and make resin particle, again with this resin particle in the water system dispersion medium, under stirring, high temperature, condition of high voltage, volatile foaming agent is immersed in this resin particle, is released to then under the low pressure atmosphere and makes.The volume density of the pre-expanded beads of manufacturing, the having or not of used weighting agent, resin density etc. are different when needing, but 0.01～0.3g/cm normally 3, and 0.015～0.18g/cm preferably 3About, normally 3～90 times of expansion ratios are also preferably about 5～60 times.In addition, the separated foam rate of this pre-expanded beads is more than 65% or 65%, and more preferably more than 80% or 80%, mean air bubble diameter is 50～1000 μ m, more preferably 100～800 μ m.Above-mentioned separated foam rate is less than 65% o'clock, and moulded products not only shrinks easily, and the turgor pressure during owing to moulding is insufficient makes fusion bonding decline, and diminishes the outward appearance of moulded products, and the tendency of resiliency decline also can take place.Also have, above-mentioned mean air bubble diameter is difficult to keep enough intensity for moulded products during less than 50 μ m, and when surpassing 1000 μ m, the superficiality of moulded products has the tendency of decline.
Pre-expanded beads of the present invention except that above-mentioned characteristic, when measuring (DSC method) with differential scanning calorimeter, has two melting peak temperatures, the melting peak heat QH at the high temperature side peak of these two melting peak temperatures, preferably 1.5～25.0J/g.Owing to two melting peak temperatures are arranged,, therefore can make pre-expanded beads foaming in mould become possibility so polyolefin resin is not crosslinked.When this melting peak heat QH did not reach 1.5J/g, the dimensional contraction of moulded products strengthened, and the mechanical properties such as compressive strength of moulded products also descend.In addition, when surpassing 25.0J/g, the surface property variation of moulded products, inner fusion bonding simultaneously is variation also, and mechanical properties descends.Particularly polyolefin resin is the occasion of polypropylene-based resin, and melting peak heat QH is 1.5～25.0J/g, and more preferably 5.0～20.0J/g particularly preferably is 8.0～18.0J/g.
By using substrate resin (polyolefin resin) to contain 1～20 weight part sterically hindered amines ethers fire retardant and high-temperature fusion peak heat is that the pre-expanded beads of 1.5～25.0J/g carries out moulding, that then can obtain having excellent flame retardancy and when burning, excellent foam-in-mould moulded products does not take place under the environment of toxic gas.
Flame-retardant polyolefin resin pre-expanded beads of the present invention is the resin with two melting peak temperatures when measuring with the DSC method, but has no particular limits for the relation between these two melting peak temperatures.When the temperature head of above-mentioned two melting peaks was 10～20 ℃, easy fusion bonding during the moulding heating was so be preferred.Two melting peak temperatures in the expanded particle, because of the molecular structure of substrate resin, the thermal history of resin, foam dosage, blowing temperature, blow(ing) pressure etc. change, still, the temperature head of two melting peaks strengthens when high temperature side foams.
Above-mentioned two melting peaks that occur on the DSC curve of pre-expanded beads, be because by when resin particle foams, carry out chilling after being heated to substrate resin near its fusing point and change substrate resin crystalline state produced, consequently obtained having the pre-expanded beads of two melting peaks.
As mentioned above, the fusion heat QH at the high temperature side peak of pre-expanded beads changes because of the molecular structure of resin and the amount of additive, but generally speaking, QH diminishes when improving blowing temperature.In the manufacture method of above-mentioned pre-expanded beads, the fusing point of the particle of substrate resin (polyolefin resin) as Tm (℃) time, the Heating temperature of pre-expanded beads is set in the scope of [(Tm-25)～(Tm+25)] ℃, and then can easily obtain high temperature side melting peak heat QH is the pre-expanded beads of 1.5J/g～25.0J/g.The reason of blowing temperature in above-mentioned scope is because according to the kind of polyolefin resin, used foaming dosage, suitably select just can produce desired pre-expanded beads as the expansion ratio of the expanded particle of target.
Below, the manufacture method of flame-retardant polyolefin resin pre-expanded beads of the present invention is described.
Usually, for the ease of in pre-frothing, using, be with polyolefin resin, earlier carry out fusion with forcing machine, kneader, banbury mixers, roller etc., that forming process becomes is cylindric, ellipticity, spherical, cubic, desirable particle shape such as rectangular-shaped, and the median size of this particle reaches 0.1～10mm, preferred 0.7～5mm.Fire retardant and the compositions such as additive that add on demand add in the fused resin in the manufacturing processed of resin usually.
There is no particular limitation for the manufacture method of flame-retardant polyolefin resin pre-expanded beads of the present invention, can use known method.For example, by in pressure vessel the flame-retardant polyolefin resin particle being dispersed in water is to form dispersion liquid in the aqueous dispersion medium of representative, while stirring whipping agent is immersed in the resin particle, add depress the temperature that this dispersion liquid is heated to regulation after, this water dispersion is released to the area of low pressure makes methods such as resin particle foaming and make.
As above-mentioned whipping agent, can enumerate, for example aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane; Inorganic gass such as volatile foaming agent such as alicyclic hydro carbons such as tetramethylene, pentamethylene, hexanaphthene and carbonic acid gas, nitrogen, air also have water etc.These both can use separately also and two or more can be used in combination.The usage quantity of whipping agent does not limit especially, as long as use according to the foam degrees of desirable flame-retardant polyolefin resin pre-expanded beads is an amount of, but, for example in the occasion of aliphatic hydrocarbon and alicyclic hydro carbons, usually, are 5～50 weight parts with respect to flame-retardant polyolefin resin particle 100 weight parts.
When the above-mentioned water dispersion of preparation, as dispersion agent, for example, can use tricalcium phosphate, magnesium basic carbonate, lime carbonate etc., can use a spot of tensio-active agent as dispersing auxiliary, for example Sodium dodecylbenzene sulfonate, n-paraffin sodium sulfonate, alpha-olefin sodium sulfonate etc.These both can use separately also respectively and can two or more be used in combination.The usage quantity of dispersion agent and tensio-active agent, according to the kind of its kind and used flame-retardant polyolefin resin particle and usage quantity etc. and different, but usually with respect to water 100 weight parts, dispersant dosage is 0.2～3 weight part, and dosage of surfactant is 0.001～0.1 weight part.
Be dispersed in the flame-retardant polyolefin resin particle in the aqueous dispersion medium of water etc., reach good degree,, add 20～100 weight parts usually with respect to water 100 weight parts for making the dispersiveness in water.
Usually, the flame-retardant polyolefin resin particle is put in the pressure vessel, forms the aqueous liquid dispersion of resin particle with water and whipping agent, again under Heating temperature, for example than under the high temperature of the softening temperature of used polyolefin resin whipping agent being impregnated in the resin particle.The water dispersion that contains the resin particle of whipping agent, then in pressure vessel, add to depress and be heated to blowing temperature, be released to the low pressure atmosphere from the opening jet pipe of this container then by 2～10mm φ, make this polyolefin resin particle foaming, obtain flame-retardant polyolefin pre-expanded beads of the present invention.Blowing temperature, any value of the high temperature side melting peak heat QH that the DSC method that has according to the kind of used flame-retardant polyolefin resin particle, as the flame-retardant polyolefin resin pre-expanded beads of purpose is measured changes, so can not stipulate a free burial ground for the destitute, but the fusing point of measuring according to the DSC method of used flame-retardant polyolefin resin particle (melting peak temperature) is during as Tm ℃, and then the Heating temperature of pre-frothing is decided by the scope of roughly [(Tm-25)～(Tm+10)] ℃.As long as blowing temperature is in above-mentioned scope, then easily obtaining pre-expanded beads has two melting peak temperatures by the DSC method, and melting peak heat QH is the pre-expanded beads of 1.5～25.0J/g.
In addition, blow(ing) pressure is mainly selected by the expansion ratio of regulation, but roughly is 0.78～4.90MPa.
For the not restriction especially of above-mentioned pressure vessel, any container of every anti-above-mentioned pressure and temperature can use.As the object lesson of above-mentioned pressure vessel, can enumerate, for example the pressure vessel of autoclave type.
Come from the manufacturing of the interior expanded molded article of mould of pre-expanded beads of the present invention, for example can be according to the currently known methods of record in public clear 51-22951 communique of spy and special fair 6-59694 communique etc., pre-expanded beads is filled in the airtight or not airtight mould, heat by water vapor etc. again, make and carry out fusion bonding between the pre-expanded beads, thereby obtain expanded molded article as the mould.
In above-mentioned forming method, before being filled into pre-expanded beads in the mould, give this particle air pressure, perhaps when being filled into this pre-expanded beads in the mould, reach that to fill under the state more than 10% or 10% be preferred pre-expanded beads being compressed to rate of compression.
The former is that the pressurized conditions by inorganic gas etc. keeps pre-expanded beads down, then can give pre-expanded beads desirable gaseous tension, as inorganic gas, can enumerate, for example air, nitrogen, helium, neon, argon, carbonic acid gas etc.These gases both can use separately, also can be used in combination more than 2 kinds or 2 kinds.Wherein, the air that preferred generic is high, nitrogen.
The latter adopts gas under pressure that pre-expanded beads is compressed to rate of compression to reach more than 10% or 10% and be filled in the mould and realize.The rate of compression of pre-expanded beads, be the weight of the pre-expanded beads when under atmospheric pressure state, being filled into flame-retardant polyolefin resin pre-expanded beads in the mould of shaper, the weight that is compressed the pre-expanded beads when being filled in the mould is removed the value of gained, represents with following formula:
Like this, after being filled into pre-expanded beads in the forming mould, the water vapor about employing 0.06～0.42MPa heats makes fusion bonding between the particle, obtains expanded molded article in the desirable mould thus.
So operate expanded molded article in the mould that obtains, have excellent flame, appearance, physical strengths such as resiliency and shock-resistance are good, so can be used for various uses, it is suitable particularly using in automobile component and material of construction etc. requires the field of flame retardant resistance and self-extinguishing.
Below, the DSC method of using among the present invention is described.
As determinator, adopt common differential scanning calorimeter, for example can enumerate DSC-7 type of the society's system of パ-キ Application エ Le マ-(Perkin-Elmer) etc.Fusing point (melting peak) Tm of the substrate resin of flame-retardant polyolefin resin pre-expanded beads (℃) mensuration, be to use above-mentioned test set, sample to polyolefin resin 1～10mg, be warmed up to 210 ℃ with 10 ℃/minute heat-up rates, the cooling rate of following with 10 ℃/minute cools to after 40 ℃, be warmed up under 210 ℃ the condition with 10 ℃/minute heat-up rate once again and carry out, the peak temperature that shows on the DSC curve that obtains like this is fusing point Tm.
Fig. 1 illustrates the example of measuring polyolefin resin particle fusing point (Tm), and as the polyolefin resin use is that the ethene containing ratio is the ethylene-propylene random copolymer of 2.5 weight %.
The melting peak heat QH of flame-retardant polyolefin resin pre-expanded beads, it is sample for pre-expanded beads 1～10mg, adopt the said determination device to be warmed up to 10 ℃/minute heat-up rate that 210 ℃ of DSC curves that obtain try to achieve, reach the DSC curve that finishes side in 0 that peak from the gradient of the peak-to-peak DSC curve of the peak of low temperature side and high temperature side and draw the tangent line (being shown in the dotted line P of Fig. 2) that is used for determining melting peak heat QH to high temperature side.For the measuring method of fusion heat QH that the high temperature side melting peak is shown, adopting used polypropylene-based resin among Fig. 1, the melting curve that the differential scanning calorimetric measurement by the preexpanded particles of polylefin resin that obtains among the embodiment 1 obtains is shown in Fig. 2.
Below, according to embodiment and comparative example explanation the present invention, but the present invention is not limited to these.And, if do not specify then " part " expression " weight part ".
Evaluation in embodiment and the comparative example is carried out according to following method.
(melting peak heat QH)
As differential scanning calorimeter, use the DSC-7 type of society's system of パ-キ Application エ Le マ-(Perkin-Elmer), sample for preexpanded particles of polylefin resin 1～10mg, be warmed up to 210 ℃ with 10 ℃/minute heat-up rates, reach the DSC curve that finishes side in 0 that peak from the gradient of the peak-to-peak DSC curve of the peak of low temperature side and high temperature side and draw tangent line (straight line P) to high temperature side, obtain the area of the part that DSC curve and tangent line be surrounded, and obtain the heat of per unit weight from the heat of trying to achieve thus.
(volume density)
Use 10000cm 3Charging basket, ask the correct weight W (g) of pre-expanded beads 10L and obtain the volume density D (g/cm of pre-expanded beads by following formula 3).
D = W 10000
(average bubble diameter)
From the pre-expanded beads that obtains, at random take out 30 pre-expanded beads, measure bubble diameter, calculate average bubble diameter again according to JIS K6402.
(separated foam rate)
Use air comparison expression specific gravity hydrometer (BECKMAN society system 930 types), obtain the separated foam volume of the pre-expanded beads that obtains, the apparent volume of trying to achieve with other alcohol dipping method removes this separated foam volume again, calculates the separated foam rate thus.
(fusion bonding rate)
Moulded products is broken, observed its section, obtain the ratio of fracture population, and estimate by following standard to the total number of particles of section.
Usually, the standard of the fusion bonding rate that should satisfy as moulded products is 60% at least.
◎: the ratio of fracture particle is more than 80% or 80%
Zero: the fracture particle ratio be 60～80% less than
*: the fracture particle ratio be 60% less than
(dimensional contraction rate)
With the size of vernier callipers mensuration moulded products, calculate shrinking percentage, and estimate by following standard with respect to mould.
Zero: shrinking percentage 3% less than
: shrinking percentage 3%～5% less than
*: more than the shrinking percentage 5% or 5%
(flame retardant resistance)
Estimate according to UL-94 hydraulic test method, and estimate by following standard.
◎: HF-1 is qualified
Zero: HF-2 is qualified
*: HF-2 is defective
(appearance)
The moulded products surface that detects by an unaided eye, and estimate by following standard.
Zero: surperficial no concave-convex, also almost very close to each other between each particle
*: the surface has concavo-convex, and very big gap is arranged between each particle
Embodiment 1～10 and comparative example 1
With ethylene-propylene random copolymer (the ethene containing ratio is 2.5 weight %), MI=6.0g/10 minute) 100 parts and by chemical formula (3):
RNHCH 2CH 2CH 2NRCH 2CH 2NHCH 2CH 2CH 2NHR????(3)
(in the formula, R represents by following formula:
The base of expression) the sterically hindered phenol ethers fire retardant (trade(brand)name: CGL116 of expression, チ バ ス ペ シ ヤ Le テ イ ケ ミ カ Le ズ (Ciba Specialty Chemicals) and mixed by the amount shown in the table 1 as the carbon black of tinting material, adopt again the single shaft forcing machine mixing after in addition granulation, make resin particle (1.8mg/ grain).The fusing point of the polyolefin resin particle that obtains is 147.3 ℃.
9.3 parts of 100 parts of this resin particles and Trimethylmethanes are put in 10 liters of pressure vessels with the dispersion agent water of 2 parts of powdery alkali formula tricalcium phosphates and 0.05 part of n-paraffin sodium sulfonate (contain 300 parts), this internal tank is heated to the blowing temperature shown in the table 1.Then, container inner pressure is controlled to the blow(ing) pressure (1.30～1.69MPa) that is pressed into the Trimethylmethane defined.Then, keep container inner pressure, open the valve of pressure vessel bottom, and water dispersion is released in the atmosphere, obtain having the pre-expanded beads of characteristic shown in the table 1 thus through the orifice plate of aperture 4.0mm φ with nitrogen.The pre-expanded beads that obtains is estimated.
With the pre-expanded beads that obtains to be filled into more than rate of compression 10% or 10% in the mould of 450mm * 300mm * 60mm, be 10 seconds of water vapor heating pre-expanded beads of 0.24～0.40MPa again with pressure, carry out fusion bonding, obtain expanded molded article in the mould.Expanded molded article in the mould that obtains is estimated.
The results are shown in the table 1.
Table 1
The embodiment numbering Additive is formed (part) Blowing temperature (℃) The characteristic of pre-expanded beads The characteristic of expanded molded article in the mould
????CGL ????116 Carbon black Dissolve peak heat QH (J/g) Volume density (g/cm 3) Bubble diameter (μ m) Separated foam rate (%) Density (g/cm 3) Fusion bonding The dimensional contraction rate Flame retardant resistance Appearance
?1 ?2 ?3 ?4 ?5 ?6 ?7 ?8 ?9 ?10 ????2 ????2 ????2 ????2 ????5 ????10 ????10 ????2 ????2 ????25 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????0.3 ????146.5 ????146.7 ????146.1 ????147.5 ????146.1 ????146.1 ????146.1 ????151.0 ????142.5 ????146.1 ??15.0 ??15.0 ??17.0 ??15.6 ??16.7 ??9.5 ??14.5 ??1.4 ??25.9 ??13.2 ????0.033 ????0.040 ????0.051 ????0.063 ????0.032 ????0.023 ????0.045 ????0.037 ????0.038 ????0.046 ?286 ?292 ?265 ?284 ?270 ?254 ?226 ?296 ?230 ?165 ??98.8 ??98.4 ??98.6 ??98.2 ??98.6 ??98.2 ??98.4 ??98.2 ??98.4 ??98.7 ??0.040 ??0.048 ??0.061 ??0.077 ??0.038 ??0.027 ??0.054 ??0.044 ??0.046 ??0.055 ◎ ◎ ○ ○ ○ ◎ ◎ ◎ × × ○ ○ ○ ○ ○ ○ ○ × ○ △ ◎ ◎ ○ ○ ◎ ◎ ◎ ○ ◎ ◎ ○ ○ ○ ○ ○ ○ ○ ○ × ×
Comparative example 1 ????0 ????0.3 ????146.5 ??14.8 ????0.038 ?320 ??98.6 ??0.045 ◎ ○ × ○
Industrial practicality
Flame-retardant polyolefin resin pre-expanded beads of the present invention because contained fire retardant is non-halogen fire retardant, therefore, does not use the problem (toxic gas etc. occurs during burning) of halogen fire retardant occasion. In addition, also the not decline of foaming in company's alveolation of using the seen bubble of mineral-type non-halogen flame retardant occasion and mould that miniaturization causes has foaming and anti-flammability in the good mould.

Claims (7)

1. flame-retardant polyolefin resin pre-expanded beads, it is to be made of the polyolefin resin composition that contains polyolefin resin and sterically hindered amines ethers fire retardant.
2. according to the described flame-retardant polyolefin resin of claim 1 pre-expanded beads, wherein said sterically hindered amines ethers fire retardant is the compound with general formula (1) expression:
R 1NHCH 2CH 2CH 2NR 2CH 2CH 2NR 3CH 2CH 2CH 2NHR 4???????(1)
[in the formula, R 1And R 2Be with general formula (2):
(R in the formula 5Be alkyl with 1～12 of carbonatoms, R 6Be methyl, cyclohexyl or octyl group) expression s-triazine part T, R 3And R 4In a kind of be with general formula (2) expression s-triazine part T, R 3And R 4In another kind then represent hydrogen atom].
3. according to claim 1 or 2 described flame-retardant polyolefin resin pre-expanded beads, the consumption of wherein said fire retardant is 10～20 weight parts with respect to polyolefin resin 100 weight parts.
4. according to claim 1,2 or 3 described flame-retardant polyolefin resin pre-expanded beads, wherein said polyolefin resin is a polypropylene-based resin.
5. flame-retardant polyolefin resin pre-expanded beads, it is the pre-expanded beads that is made of the polyolefin resin composition that contains polyolefin resin and sterically hindered amines ethers fire retardant, this pre-expanded beads is when measuring with differential scanning calorimeter, demonstrate 2 melting peaks on the DSC curve, the melting peak heat QH at the high temperature side peak of these 2 melting peaks is 1.5～25.0J/g.
6. according to the described flame-retardant polyolefin resin of claim 5 pre-expanded beads, wherein said polyolefin resin is a polypropylene-based resin.
7. expanded molded article in the mould, it carries out in the mould foaming with each described flame-retardant polyolefin resin pre-expanded beads of claim 1～6 and makes.
CNB028241800A 2001-12-03 2002-11-29 Pre-expanded beads of flame-retardant polyolefin resin and molded object thereof by in-mold foaming Expired - Lifetime CN1309768C (en)

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Cited By (6)

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CN101248120B (en) * 2005-08-23 2011-04-06 巴斯夫欧洲公司 Method for producing foamed slabs
CN102388093A (en) * 2009-04-15 2012-03-21 株式会社钟化 Polyolefin resin pre-expanded particles and polyolefin resin in-mold expansion-molded article comprising polyolefin resin pre-expanded particles
CN102388093B (en) * 2009-04-15 2013-10-23 株式会社钟化 Polyolefin resin pre-expanded particles and polyolefin resin in-mold expansion-molded article comprising polyolefin resin pre-expanded particles
US10072128B2 (en) 2009-04-15 2018-09-11 Kaneka Corporation Polyolefin-based resin pre-expanded particles and polyolefin-based resin in-mold expansion molded article comprising polyolefin-based resin pre- expanded particles
CN103097451A (en) * 2010-08-30 2013-05-08 Kaneka比利时公司 Expanded polyolefin containing powdered activated carbon
CN103097451B (en) * 2010-08-30 2016-03-30 Kaneka比利时公司 Expanded polyolefin containing powdered activated carbon

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US20030105194A1 (en) 2003-06-05
EP1454947A4 (en) 2006-12-20
EP1454947A1 (en) 2004-09-08
JPWO2003048239A1 (en) 2005-04-14
DE60235399D1 (en) 2010-04-01
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WO2003048239A1 (en) 2003-06-12
CN1309768C (en) 2007-04-11

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